Organometal catalyst compositions

ABSTRACT

This invention provides compositions that are useful for polymerizing at least one monomer to produce a polymer. This invention also provides compositions that are useful for polymerizing at least one monomer to produce a polymer, wherein said composition comprises a post-contacted organometal compound, a post-contacted organoaluminum compound, and a post-contacted treated solid oxide compound.

FIELD OF THE INVENTION

[0001] This invention is related to the field of organometal catalystcompositions.

BACKGROUND OF THE INVENTION

[0002] The production of polymers is a multi-billion dollar business.This business produces billions of pounds of polymers each year.Millions of dollars have been spent on developing technologies that canadd value to this business.

[0003] One of these technologies is called metallocene catalysttechnology. Metallocene catalysts have been known since about 1958.However, their low productivity did not allow them to be commercialized.About 1975, it was discovered that contacting one part water with onepart trimethylaluminum to form methyl aluminoxane, and then contactingsuch methyl aluminoxane with a metallocene compound, formed ametallocene catalyst that had greater activity. However, it was soonrealized that large amounts of expensive methyl aluminoxane were neededto form an active metallocene catalyst. This has been a significantimpediment to the commercialization of metallocene catalysts.

[0004] Fluoro-organo borate compounds have been used in place of largeamounts of methyl aluminoxane. However, this is not satisfactory, sincesuch borate compounds are very sensitive to poisons and decomposition,and can also be very expensive.

[0005] It should also be noted that having a heterogeneous catalyst isimportant. This is because heterogeneous catalysts are required for mostmodern commercial polymerization processes. Furthermore, heterogeneouscatalysts can lead to the formation of substantially uniform polymerparticles that have a high bulk density. These types of substantiallyuniformed particles are desirable because they improve the efficiency ofpolymer production and transportation. Efforts have been made to produceheterogeneous metallocene catalysts; however, these catalysts have notbeen entirely satisfactory.

[0006] Therefore, the inventors provide this invention to help solvethese problems.

SUMMARY OF THE INVENTION

[0007] An object of this invention is to provide a process that producesa catalyst composition that can be used to polymerize at least onemonomer to produce a polymer.

[0008] Another object of this invention is to provide the catalystcomposition.

[0009] Another object of this invention is to provide a processcomprising contacting at least one monomer and the composition underpolymerization conditions to produce the polymer.

[0010] Another object of this invention is to provide an article thatcomprises the polymer produced with the catalyst composition of thisinvention.

[0011] In accordance with one embodiment of this invention, a process toproduce a catalyst composition is provided. The process comprises (oroptionally, “consists essentially of”, or “consists of”) contacting anorganometal compound, an organoaluminum compound, and a treated solidoxide compound to produce the catalyst composition,

[0012] wherein the organometal compound has the following generalformula:

(X¹)(X²)(X³)(X⁴)M¹

[0013] wherein M¹ is selected from the group consisting of titanium,zirconium, and hafnium;

[0014] wherein (X¹) is independently selected from the group consistingof cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls;

[0015] wherein substituents on the substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls of (X¹) are selectedfrom the group consisting of aliphatic groups, cyclic groups,combinations of aliphatic and cyclic groups, silyl groups, alkyl halidegroups, halides, organometallic groups, phosphorus groups, nitrogengroups, silicon, phosphorus, boron, germanium, and hydrogen;

[0016] wherein at least one substituent on (X¹) can be a bridging groupwhich connects (X¹) and (X²);

[0017] wherein (X³) and (X⁴) are independently selected from the groupconsisting of halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;

[0018] wherein (X²) is selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, substituted fluorenyls, halides, aliphatic groups,substituted aliphatic groups, cyclic groups, substituted cyclic groups,combinations of aliphatic groups and cyclic groups, combinations ofsubstituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic groups and substituted cyclic groups, amidogroups, substituted amido groups, phosphido groups, substitutedphosphido groups, alkyloxide groups, substituted alkyloxide groups,aryloxide groups, substituted aryloxide groups, organometallic groups,and substituted organometallic groups;

[0019] wherein substituents on (X²) are selected from the groupconsisting of aliphatic groups, cyclic groups, combinations of aliphaticgroups and cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen;

[0020] wherein at least one substituent on (X²) can be a bridging groupwhich connects (X¹) and (X²);

[0021] wherein the organoaluminum compound has the following generalformula:

Al(X⁵ )_(n)(X⁶)_(3−n)

[0022] wherein (X⁵) is a hydrocarbyl having from 1 to about 20 carbonatoms;

[0023] wherein (X⁶) is a halide, hydride, or alkoxide; and

[0024] wherein “n” is a number from 1 to 3 inclusive;

[0025] wherein the treated solid oxide compound comprises fluorine,boron, and a solid oxide compound;

[0026] wherein the solid oxide compound comprises silica, and there is asubstantial absence of aluminum, titanium, or zirconium.

[0027] In accordance with another embodiment of this invention, aprocess is provided comprising contacting at least one monomer and thecatalyst composition under polymerization condition to produce apolymer.

[0028] In accordance with another embodiment of this invention, anarticle is provided. The article comprises the polymer produced inaccordance with this invention.

[0029] These objects, and other objects, will become more apparent tothose with ordinary skill in the art after reading this disclosure.

DETAILED DESCRIPTION OF THE INVENTION

[0030] Organometal compounds used in this invention have the followinggeneral formula:

(X¹)(X²)(X³)(X⁴)M¹

[0031] In this formula, M¹ is selected from the group consisting oftitanium, zirconium, and hafnium. Currently, it is most preferred whenM¹ is zirconium.

[0032] In this formula, (X¹) is independently selected from the groupconsisting of (hereafter “Group OMC-I”) cyclopentadienyls, indenyls,fluorenyls, substituted cyclopentadienyls, substituted indenyls, suchas, for example, tetrahydroindenyls, and substituted fluorenyls, suchas, for example, octahydrofluorenyls.

[0033] Substituents on the substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls of (X¹) can be selectedindependently from the group consisting of aliphatic groups, cyclicgroups, combinations of aliphatic and cyclic groups, silyl groups, alkylhalide groups, halides, organometallic groups, phosphorus groups,nitrogen groups, silicon, phosphorus, boron, germanium, and hydrogen, aslong as these groups do not substantially, and adversely, affect thepolymerization activity of the composition.

[0034] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes.Substituted silyl groups include, but are not limited to, alkylsilylgroups where each alkyl group contains from 1 to about 12 carbon atoms,arylsilyl groups, and arylalkylsilyl groups. Suitable alkyl halidegroups have alkyl groups with 1 to about 12 carbon atoms. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

[0035] Suitable examples of such substituents are methyl, ethyl, propyl,butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl,octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl,chloro, bromo, iodo, trimethylsilyl, and phenyloctylsilyl.

[0036] In this formula, (X³) and (X⁴) are independently selected fromthe group consisting of (hereafter “Group OMC-II”) halides, aliphaticgroups, substituted aliphatic groups, cyclic groups, substituted cyclicgroups, combinations of aliphatic groups and cyclic groups, combinationsof substituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic and substituted cyclic groups, amido groups,substituted amido groups, phosphido groups, substituted phosphidogroups, alkyloxide groups, substituted alkyloxide groups, aryloxidegroups, substituted aryloxide groups, organometallic groups, andsubstituted organometallic groups, as long as these groups do notsubstantially, and adversely, affect the polymerization activity of thecomposition.

[0037] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes.Currently, it is preferred when (X³) and (X⁴) are selected from thegroup consisting of halides and hydrocarbyls, where such hydrocarbylshave from 1 to about 10 carbon atoms. However, it is most preferred when(X³) and (X⁴) are selected from the group consisting of fluoro, chloro,and methyl.

[0038] In this formula, (X²) can be selected from either Group OMC-I orGroup OMC-II.

[0039] At least one substituent on (X¹) or (X²) can be a bridging groupthat connects (X¹) and (X²), as long as the bridging group does notsubstantially, and adversely, affect the activity of the composition.Suitable bridging groups include, but are not limited to, aliphaticgroups, cyclic groups, combinations of aliphatic groups and cyclicgroups, phosphorous groups, nitrogen groups, organometallic groups,silicon, phosphorus, boron, and germanium.

[0040] Suitable examples of aliphatic groups are hydrocarbyls, such as,for example, paraffins and olefins. Suitable examples of cyclic groupsare cycloparaffins, cycloolefins, cycloacetylenes, and arenes. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

[0041] Various processes are known to make these organometal compounds.See, for example, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305;5,401,817; 5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636;5,565,592; 5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284;5,554,795; 5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203;5,654,454; 5,705,579; and 5,668,230; the entire disclosures of which arehereby incorporated by reference.

[0042] Specific examples of such organometal compounds are as follows:

[0043] bis(cyclopentadienyl)hafnium dichloride;

[0044] bis(cyclopentadienyl)zirconium dichloride;

[0045] 1,2-ethanediylbis(η⁵-1-indenyl)di-n-butoxyhafnium;

[0046] 1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium;

[0047] 3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafniumdichloride;

[0048] methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

[0049] bis(n-butylcyclopentadienyl)bis(di-t-butylamido)hafnium;

[0050] bis(n-butylcyclopentadienyl)zirconium dichloride;

[0051] dimethylsilylbis(1-indenyl)zirconium dichloride;

[0052] octylphenylsilylbis(1-indenyl)hafnium dichloride;

[0053] dimethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

[0054] dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride;

[0055] 1,2-ethanediylbis(9-fluorenyl)zirconium dichloride;

[0056] indenyl diethoxy titanium(IV) chloride;

[0057] (isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride;

[0058] bis(pentamethylcyclopentadienyl)zirconium dichloride;

[0059] bis(indenyl) zirconium dichloride;

[0060] methyloctylsilyl bis (9-fluorenyl) zirconium dichloride;

[0061] and

[0062] bis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate

[0063] Preferably, the organometal compound is selected from the groupconsisting of

[0064] bis(n-butylcyclopentadienyl)zirconium dichloride;

[0065] bis(indenyl)zirconium dichloride;

[0066] dimethylsilylbis(1-indenyl) zirconium dichloride;

[0067] and

[0068] methyloctylsilylbis(9-fluorenyl)zirconium dichloride

[0069] Organoaluminum compounds have the following general formula:

Al(X⁵)_(n)(X⁶)_(3−n)

[0070] In this formula, (X⁵) is a hydrocarbyl having from 1 to about 20carbon atoms. Currently, it is preferred when (X⁵) is an alkyl havingfrom 1 to about 10 carbon atoms. However, it is most preferred when (X⁵)is selected from the group consisting of methyl, ethyl, propyl, butyl,and isobutyl.

[0071] In this formula, (X⁶) is a halide, hydride, or alkoxide.Currently, it is preferred when (X⁶) is independently selected from thegroup consisting of fluoro and chloro. However, it is most preferredwhen (X⁶) is chloro.

[0072] In this formula, “n” is a number from 1 to 3 inclusive. However,it is preferred when “n” is 3.

[0073] Examples of such compounds are as follows:

[0074] trimethylaluminum;

[0075] triethylaluminum (TEA);

[0076] tripropylaluminum;

[0077] diethylaluminum ethoxide;

[0078] tributylaluminum;

[0079] diisobutylaluminum hydride;

[0080] triisobutylaluminum hydride;

[0081] triisobutylaluminum; and

[0082] diethylaluminum chloride.

[0083] Currently, TEA is preferred.

[0084] The treated solid oxide compound comprises fluorine, boron, and asolid oxide compound. The solid oxide compound comprises silica, andthere is a substantial absence of titanium and zirconium.

[0085] Suitable preformed silicas include those made by aqueousgellation and sold commercially by W. R. Grace Company, such as Davisongrade 952, and grade 951, or flame hydrolyzed silicas such as those soldunder the name of Cabosils. Suitable silicas also include those made byaqueous gellation amd subsequent drying from organic solvents, such asexemplified by U.S. Pat. No. 3,900,457, herein incorporated byreference. Suitable silicas may also be made by hydrolysis of ethyltetraorthosilicate provided that a gel thus formed is comprised ofsubstantially silica or silica-boria, as exemplified in U.S. Pat. Nos.4,301,034, 4,547,557, and 4,339,559; the entire disclosures of which areherein incorporated by reference.

[0086] To prepare the treated solid oxide compound, fluorine and boroncan be added to the solid oxide compound by any method known in the art.In addition, the fluorine and boron can be added to the solid oxidecompound in any order of steps that can produce the treated solid oxidecompound.

[0087] A boron-containing solid oxide compound can be made by aqueous oranhydrous cogellation of a silicate compound and a boron-containingcompound, or a preformed silica can be impregnated or otherwise treatedwith a boron-containing compound, such as, for example, boric acid,organic borate esters, boranes, alkyl boranes, and mixtures thereof. Aparticularly useful variation is to impregnate a preformed silica withammonium tetrafluoroborate (NH₄BF₄) or fluoroboric acid (HBF₄).

[0088] In a first method, the boron-containing solid oxide compound canbe made by any suitable method of cogelling boron from aboron-containing compound and a silicate compound. The boron can beadded to the solid oxide compound by cogellation of aqueous materials,as disclosed in U.S. Pat. Nos. 3,887,494; 3,119,569; 4,405,501;4,436,882; 4,436,883; 4,392,990; 4,081,407; 4,981,831; and 4,152,503;the entire disclosures of which are hereby incorporated by reference.For example, ethyl tetraorthosilicate can be reacted and hydrolyzed inthe presence of boric acid, a borate compound, or an organoboroncompound to produce the boron-containing solid oxide compound.Alternatively, boron-containing compounds, such as boric acid or sodiumborates, can be incorporated into silicate gels formed from an aqueouswater glass solution to produce the boron-containing solid oxidecompound.

[0089] In a second method, boron can be added to the solid oxidecompound by cogellation in an organic or anhydrous solution as disclosedin U.S. Pat. Nos. 4,301,034; 4,547,557; and 4,339,559; the entiredisclosures of which are hereby incorporated by reference.

[0090] In a third method, silicon and boron compounds can be combined byflame hydrolysis.

[0091] The preferred method is to impregnate a preformed solid oxidecompound before or after calcining with an aqueous or organic solutionof a boron-containing compound to produce the boron-containing solidoxide compound. A suitable amount of the solution is utilized to providethe desired concentration of boron after drying. The boron-containingsolid oxide compound is then dried by any suitable method known in theart. For example, the drying can be accomplished by vacuum drying, spraydrying, or flash drying.

[0092] These boron-containing solid oxide compounds produced bycogellation contain from about 0.5 to about 50% by weight boron based onthe weight of the boron-containing solid oxide compound beforecalcining, preferably from about 1 to about 20 weight percent boron, andmost preferably from 2 to 10 weight percent boron. The boron-containingsolid oxide compounds can also contain minor amounts of othercomponents, provided that the do not interfere with their use as anactivator for the organometal compounds. Other minor components include,but are not limited to, iron, calcium, chromium, vanadium, zinc, nickel,phosphate, magnesium, and the like.

[0093] The solid oxide compound should have a pore volume greater thanabout 0.5 cc/g, preferably greater than about 0.8 cc/g, and mostpreferably, greater than 1.0 cc/g.

[0094] The solid oxide compound should have a surface area aftercalcining at 500° C. in a range of about 100 to about 1000 m²/g,preferably from about 200 to about 800 m²/g, and most preferably, from250 to 600 m²/g.

[0095] Any boron-containing compound known in the art that canimpregnate the solid oxide compound with boron can be used in thisinvention. The boron-containing compound can include, but is not limitedto, boric acid (H₃BO₃), sodium borate (Na₃BO₃), boron propoxide(B(OC₃H₇)₃), triethylborane (B(C₂H₅)₃), boroxines, boron hydrides, andmixtures thereof.

[0096] When impregnating a preformed silica with a boron-containingcompound, generally, the amount of boron present is in a range of about0.1 to about 10 millimoles per gram of boron-containing solid oxidecompound before calcining or the amount added to a precalcined solidoxide compound. Preferably, the amount of boron present in theboron-containing solid oxide compound is in a range of about 0.5 toabout 5 millimoles per gram of boron-containing solid oxide compoundbefore calcining or the amount added to a precalcined solid oxidecompound. Most preferably, the amount of boron present is in a range of1 to 3 millimoles per gram of boron-containing solid oxide compoundbefore calcining or the amount added to a precalcined solid oxidecompound.

[0097] In at least one step in the production of the treated solid oxidecompound, calcining occurs. Generally, calcining is conducted for about1 minute to about 100 hours, preferably for about 1 hour to about 50hours, and most preferably, from 3 hours to 20 hours. The calcining isconducted at a temperature in a range of about 150 to about 900° C.,preferably, in a range of about 200 to about 700° C., and mostpreferably, in a range of 250 to 500° C. Any type of suitable atmospherecan be used during calcining. Generally, calcining can be completed inan inert atmosphere. Alternatively, an oxiding atmosphere, such as, forexample, oxygen or air, or a reducing atmosphere, such as, for example,hydrogen or carbon monoxide, can be used.

[0098] To produce the treated solid oxide compound, before, during, orafter calcining, the solid oxide compound is contacted with afluorine-containing compound. Any method known in the art for contactingthe solid oxide compound with the fluorine-containing compound can beused in this invention. One common method is to impregnate the solidoxide compound with an aqueous solution of a fluorine-containing salt,such as, for example, ammonium fluoride (NH₄F), ammonium bifluoride(NH₄HF₂), hydrofluoric acid (HF), ammonium silicofluoride ((NH₄)₂SiF₆),ammonium fluoroborate (NH₄BF₄), ammonium fluorophosphate (NH₄PF₆),fluoroboric acid (HBF₄), and mixtures thereof. Alternatively, thefluorine-containing compound can be dissolved into an organic solvent,such as an alcohol, and used to impregnate the solid oxide compound tominimize shrinkage of pores during drying. Drying can be accomplished byany method known in the art such as vacuum drying, spray drying, flashdrying, and the like.

[0099] The fluorine-containing compound can also be incorporated into agel by adding it to one of the aqueous materials before gellation. Theseaqueous materials were disclosed in the first and second methods forpreparing boron-containing solid oxide compounds discussed previously inthis disclosure.

[0100] The fluorine-containing compound can also be added to a slurrycontaining a gel before drying. Formation of a gel was disclosed in thefirst and second methods for preparing boron-containing solid oxidecompounds discussed previously in this disclosure.

[0101] The fluorine-containing compound can also be added duringcalcining. In this technique, the fluoride-containing compound can bevaporized into a gas stream used to fluidize the solid oxide compound orboron-containing solid oxide compound so that it is fluorided from thegas stream. In addition to some of the fluorine-containing compoundsdescribed above, volatile organic fluorides may be used at temperaturesabove their decomposition points, or at temperatures high enough tocause reaction. For example, perfluorohexane, perfluorobenzene,trifluoroacetic acid, trifluoroacetic anhydride,hexafluoroacetylacetonate, and mixtures thereof can be vaporized andcontacted with the solid oxide compound or boron-containing solid oxidecompound at about 300 to about 600° C. in air or nitrogen. Inorganicfluoride containing vapors may also be used, such as, for example,hydrogen fluoride or even elemental fluorine gas.

[0102] The solid oxide compound or boron-containing solid oxide compoundcan also be calcined at a temperature in a range of about 100 to 900° C.before being fluorided.

[0103] Another method of producing the treated solid oxide compound isto simultaneously contact a preformed solid oxide compound prior tocalcining with a boron-containing compound, such as boric acid, and afluorine-containing compound, such as hydrofluoric acid.

[0104] A preferred method of producing the treated solid oxide compoundis to contact a preformed solid oxide compound before calcining andammonium fluoroborate (NH₄BF₄) or fluoroboric acid (HBF₄), thusincorporating the fluoride and boron into or onto the preformed solidoxide compound in one treatment.

[0105] Another preferred method of producing the treated solid oxidecompound is to first calcine the solid oxide compound producing acalcined solid oxide compound. Then, contacting the calcined solid oxidecompound with an anhydrous solution of fluoroboric acid to produced thetreated solid oxide compound. Optionally, the treated solid oxidecompound can be further calcined as discussed previously in thisdisclosure.

[0106] The amount of fluorine present in the treated solid oxidecompound is about 1 to about 50% by weight fluorine based on the weightof the treated solid oxide compound before calcining or the amount addedto a precalcined solid oxide compound. Preferably, it is about 3 toabout 25% by weight, and most preferably, it is 4 to 25% by weightfluorine based on the weight of the treated solid oxide compound beforecalcining or the amount added to a precalcined solid oxide compound.

[0107] The compositions of this invention can be produced by contactingthe organometal compound, the treated solid oxide compound, and theorganoaluminum compound, together. This contacting can occur in avariety of ways, such as, for example, blending. Furthermore, each ofthese compounds can be fed into the reactor separately, or variouscombinations of these compounds can be contacted together before beingfurther contacted in the reactor, or all three compounds can becontacted together before being introduced into the reactor.

[0108] Currently, one method is to first contact an organometal compoundand a treated solid oxide compound together, for about 1 minute to about24 hours, preferably, about 1 minute to about 1 hour, at a temperaturefrom about 10° C. to about 100° C., preferably 15° C. to 50° C., to forma first mixture, and then contact this first mixture with anorganoaluminum compound to form the catalyst composition.

[0109] Another method is to precontact the organometal compound, theorganoaluminum compound, and the treated solid oxide compound beforeinjection into a polymerization reactor for about 1 minute to about 24hours, preferably, 1 minute to 1 hour, at a temperature from about 10°C. to about 200° C., preferably 20° C. to 80° C. to produce the catalystcomposition.

[0110] A weight ratio of the organoaluminum compound to the treatedsolid oxide compound in the catalyst composition ranges from about 5:1to about 1:1000, preferably, from about 3:1 to about 1:100, and mostpreferably, from 1:1 to 1:50.

[0111] A weight ratio of the treated solid oxide compound to theorganometal compound in the composition ranges from about 10,000:1 toabout 1:1, preferably, from about 1000:1 to about 10:1, and mostpreferably, from 250:1 to 20:1. These ratios are based on the amount ofthe components combined to give the catalyst composition.

[0112] After contacting, the catalyst composition comprises apost-contacted organometal compound, a post-contacted organoaluminumcompound, and a post-contacted treated solid oxide compound. Preferably,the post-contacted treated solid oxide compound is the majority, byweight, of the composition. Often times, specific components of acatalyst are not known, therefore, for this invention, the catalystcomposition is described as comprising post-contacted compounds.

[0113] A weight ratio of the post-contacted organoaluminum compound tothe post-contacted treated solid oxide compound in the catalystcomposition ranges from about 5:1 to about 1:1000, preferably, fromabout 3:1 to about 1:100, and most preferably, from 1:1 to 1:50.

[0114] A weight ratio of the post-contacted treated solid oxide compoundto the post-contacted organometal compound in the catalyst compositionranges from about 10,000:1 to about 1:1, preferably, from about 1000:1to about 10:1, and most preferably, from 250:1 to 20:1.

[0115] The catalyst composition of this invention has an activitygreater than a catalyst composition that uses the same organometalcompound, and the same organoaluminum compound, but uses silica,fluorided silica, or silica-boria as an activator for the organometalcompound as shown in comparative examples 2-4. The activity is measuredunder slurry polymerization conditions, using isobutane as the diluent,and with a polymerization temperature of about 50 to about 110° C., andan ethylene pressure of about 400 to about 800 psig. When comparingactivities, the polymerization runs should occur at the samepolymerization conditions. The reactor should have substantially noindication of any wall scale, coating or other forms of fouling.

[0116] However, it is preferred if the activity is greater than about100 grams of polymer per gram of treated solid oxide compound per hour,more preferably greater than about 500, and most preferably greater than1000. This activity is measured under slurry polymerization conditions,using isobutane as the diluent, and with a polymerization temperature of90° C., and an ethylene pressure of 550 psig. The reactor should havesubstantially no indication of any wall scale, coating or other forms offouling.

[0117] One of the important aspects of this invention is that noaluminoxane needs to be used in order to form the catalyst composition.Aluminoxane is an expensive compound that greatly increases polymerproduction costs. This also means that no water is needed to help formsuch aluminoxanes. This is beneficial because water can sometimes kill apolymerization process. Additionally, it should be noted that nofluoro-organo borate compounds need to be used in order to form thecatalyst composition. Examples of such fluoro-organo borate compoundsthat are not needed in this invention include, but are not limited to,fluorinated aryl borates, such as, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)boron,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, andmixtures thereof. The above examples and related fluoro-organo boratecompounds are thought to form “weakly-coordinating” anions when combinedwith metallocene catalysts as disclosed in U.S. Pat. No. 5,919,983. Theboron compounds of this invention are distinguished from those prior artfluoro-organo borate compounds described previously in that they areinorganic when the treated solid oxide compound is formed, eitherthrough the direct use of an inorganic borate or by calciningorganoboron compounds to boron oxides. In summary, this means that thetreated solid oxide compound, unlike the prior art fluoro-organo boratecompounds described above, is inorganic and heterogenous in diluentsduring polymerization. They can be used for polymerizing monomers andcan be easily and inexpensively produced because of the substantialabsence of any aluminoxane compounds or fluoro-organo borate compounds.Additionally, no organochromium compounds or MgCl₂ need to be added toform the invention. Although aluminoxane, fluoro-organo boratecompounds, organochromium compounds, or MgCl₂ are not needed in thepreferred embodiments to produce the catalyst composition, thesecompounds can be used in other embodiments of this invention.

[0118] In another embodiment of this invention, a process comprisingcontacting at least one monomer and the catalyst composition to produceat least one polymer is provided. The term “polymer” as used in thisdisclosure includes homopolymers and copolymers. The catalystcomposition can be used to polymerize at least one monomer to produce ahomopolymer or a copolymer. Usually, homopolymers are comprised ofmonomer residues, having 2 to about 20 carbon atoms per molecule,preferably 2 to about 10 carbon atoms per molecule. Currently, it ispreferred when at least one monomer is selected from the groupconsisting of ethylene, propylene, 1-butene, 3-methyl-1-butene,1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixturesthereof

[0119] When a homopolymer is desired, it is most preferred to polymerizeethylene or propylene. When a copolymer is desired, the copolymercomprises monomer residues and one or more comonomer residues, eachhaving from about 2 to about 20 carbon atoms per molecule. Suitablecomonomers include, but are not limited to, aliphatic 1-olefins havingfrom 3 to 20 carbon atoms per molecule, such as, for example, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and otherolefins and conjugated or nonconjugated diolefins such as 1,3-butadiene,isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene,1,7-hexadiene, and other such diolefins and mixtures thereof. When acopolymer is desired, it is preferred to polymerize ethylene and atleast one comonomer selected from the group consisting of 1-butene,1-pentene, 1-hexene, 1-octene, and 1-decene. The amount of comonomerintroduced into a reactor zone to produce a copolymer is generally fromabout 0.01 to about 10 weight percent comonomer based on the totalweight of the monomer and comonomer, preferably, about 0.01 to about 5,and most preferably, 0.1 to 4. Alternatively, an amount sufficient togive the above described concentrations, by weight, in the copolymerproduced can be used.

[0120] Processes that can polymerize at least one monomer to produce apolymer are known in the art, such as, for example, slurrypolymerization, gas phase polymerization, and solution polymerization.It is preferred to perform a slurry polymerization in a loop reactionzone. Suitable diluents used in slurry polymerization are well known inthe art and include hydrocarbons which are liquid under reactionconditions. The term “diluent” as used in this disclosure does notnecessarily mean an inert material; it is possible that a diluent cancontribute to polymerization. Suitable hydrocarbons include, but are notlimited to, cyclohexane, isobutane, n-butane, propane, n-pentane,isopentane, neopentane, and n-hexane. Furthermore, it is most preferredto use isobutane as the diluent in a slurry polymerization. Examples ofsuch technology can be found in U.S. Pat. Nos. 4,424,341; 4,501,885;4,613,484; 4,737,280; and 5,597,892; the entire disclosures of which arehereby incorporated by reference.

[0121] The catalyst compositions used in this process produce goodquality polymer particles without substantially fouling the reactor.When the catalyst composition is to be used in a loop reactor zone underslurry polymerization conditions, it is preferred when the particle sizeof the solid oxide compound is in a range of about 10 to about 1000microns, preferably about 25 to about 500 microns, and most preferably,50 to 200 microns, for best control during polymerization.

[0122] In a more specific embodiment of this invention, a process isprovided to produce a catalyst composition, the process comprising(optionally, “consisting essentially of”, or “consisting of”):

[0123] (1) contacting silica with an aqueous solution containingammonium fluoroborate or fluoroboric acid to produce a fluorided,boron-containing solid oxide compound having from 1 to 3 millimoles ofboron per gram of fluorided, boron-containing solid oxide compoundbefore calcining and 4 to 25% by weight fluorine based on the weight ofthe boron-containing solid oxide compound before calcining;

[0124] (2) calcining the fluorided, boron-containing solid oxidecompound at a temperature within a range of 250 to 500° C. for 3 to 20hours to produce a calcined composition;

[0125] (3) combining the calcined composition andbis(n-butylcyclopentadienyl) zirconium dichloride at a temperaturewithin a range of 15° C. to 50° C. for 1 minute to 1 hour to produce amixture; and

[0126] (4) combining the mixture and triethylaluminum to produce thecatalyst composition.

[0127] Hydrogen can be used with this invention in a polymerizationprocess to control polymer molecular weight.

[0128] After the polymers are produced, they can be formed into variousarticles, such as, for example, household containers and utensils, filmproducts, drums, fuel tanks, pipes, geomembranes, and liners. Variousprocesses can form these articles. Usually, additives and modifiers areadded to the polymer in order to provide desired effects. It is believedthat by using the invention described herein, articles can be producedat a lower cost, while maintaining most, if not all, of the uniqueproperties of polymers produced with metallocene catalysts.

EXAMPLES

[0129] Calcining

[0130] About 10 grams of an oxide compound were placed in a 1.75 inchquartz tube fitted with a sintered quartz disk at the bottom. While theoxide compound was supported on the disk, dry air was blown up throughthe disk at the linear rate of about 1.6 to about 1.8 standard cubicfeet per hour. An electric furnace around the quartz tube was thenturned on, and the temperature was raised at the rate of about 400° C.per hour to the indicated temperature, such as 600° C. At thattemperature, the oxide compound was allowed to fluidize for three hoursin the dry air. Afterward, the oxide compound was collected and storedunder dry nitrogen, where it was protected from the atmosphere untilready for testing. It was never allowed to experience any exposure tothe atmosphere.

[0131] Polymerization Runs

[0132] Polymerization runs were made in a 2.2 liter steel reactorequipped with a marine stirrer running at 400 revolutions per minute(rpm). The reactor was surrounded by a steel jacket containing boilingmethanol with a connection to a steel condenser. The boiling point ofthe methanol was controlled by varying nitrogen pressure applied to thecondenser and jacket, which permitted precise temperature control towithin half a degree centigrade, with the help of electronic controlinstruments.

[0133] Unless otherwise stated, first, a small amount (0.01 to 0.10grams normally) of an oxide compound or the inventive treated solidoxide compound was charged under nitrogen to the dry reactor. Next, 2.0milliliters of a toluene solution containing 0.5 percent by weight ofbis(n-butylcyclopentadienyl) zirconium dichloride were added, followedby 0.6 liters of isobutane liquid. Then, 1.0 milliliter of a 1.0 molarsolution of triethylaluminum (TEA) was added, followed by another 0.6liters of isobutane liquid. The reactor was heated up to the specifiedtemperature, typically to 90° C. Finally, ethylene was added to thereactor to equal a fixed pressure of about 550 psig to produce areaction mixture. The reaction mixture was allowed to stir for usuallyabout one hour. As ethylene was consumed, more ethylene flowed in tomaintain the pressure. The activity was noted by recording the flow ofethylene into the reactor to maintain the set pressure.

[0134] After the allotted time, the ethylene flow was stopped, and thereactor slowly depressurized and opened to recover a granular polymer.In all cases, the reactor was clean with no indication of any wallscale, coating or other forms of fouling. The polymer was then removedand weighed. Activity was specified as grams of polymer produced pergram of oxide compound or treated solid oxide compound charged per hour.

[0135] Description of Results

[0136] Control and inventive examples are described below. The resultsof these polymerization tests are listed in Tables 1 and 2.

[0137] Control Example 1 (No Oxide Compound)

[0138] A polymerization run was made in the absence of any oxidecompound by the procedure discussed previously. No polymer was found inthe reactor, and no ethylene consumption was detected.

[0139] Control Example 2 (Silica)

[0140] Grade 952 silica was obtained from W. R. Grace having a porevolume of about 1.6 cc/g and a surface area of about 300 m²/g. A sampleof the silica was calcined at 600° C. in dry air for three hours asdescribed previously to produce a calcined silica. The calcined silicawas then tested for polymerization activity with an organometal compoundand TEA. The calcined silica yielded only 1 gram of polymer per gram ofcalcined silica per hour.

[0141] Control Example 3 (Fluorided Silica)

[0142] A 33.82 gram sample of the same grade 952 silica described inExample 2 was impregnated with 70 milliliters of an aqueous solutioncontaining 3.45 grams of ammonium bifluoride to produce a fluoridedsilica. Then, the fluorided silica was dried under vacuum at 120° C.overnight. A sample of the fluorided silica was calcined in dry air at450° C. for three hours. It was then tested for polymerization activitywith TEA and an organometal compound, but it yielded no polymer.

[0143] Control Example 4 (Silica-Boria)

[0144] A 10.3 gram sample of W. R. Grace grade 952 silica wasimpregnated with 20 milliliters of a solution containing 0.021 moles ofboric acid to produce a silica-boria. It was then dried under vacuum at120° C. overnight, and a sample of the silica-boria was calcined in dryair at 400° C. for three hours. When tested for polymerization activity,the silica-boria produced 12 grams of polymer per gram of silica-boriaper hour.

[0145] Inventive Examples 5-7 (Treated solid oxide compound)

[0146] A 10.3 gram sample of W. R. Grace grade 952 silica wasimpregnated with 20 milliliters of an aqueous solution containing 0.021moles of boric acid and 1.0 grams of ammonium bifluoride to produce afluorided, boron-containing solid oxide compound. It was then driedunder vacuum at 120° C. overnight, and three different samples of thefluorided, boron-containing solid oxide compound were calcined in dryair for three hours at 300° C., 400° C., and 500° C. to produce atreated solid oxide compound. When tested for polymerization activity,these samples produced 490, 305, and 161 grams of polymer per gram oftreated solid oxide compound per hour respectively.

[0147] Inventive Example 8 (Treated Solid Oxide Compound)

[0148] A 12.5 gram sample of 12.5 grams of W. R. Grace grade 952 silicawas impregnated with 25 milliliters of an aqueous solution containing0.015 moles of fluoroboric acid (HBF₄) to produce a fluorided,boron-containing solid oxide compound. It was then dried under vacuum at120° C. overnight, and a sample was calcined in dry air for three hoursat 250° C. to produce a treated solid oxide compound. When tested forpolymerization activity, the treated solid oxide compound produced 544grams of polymer per gram of treated solid oxide compound per hour.

[0149] Inventive Example 9 (Treated Solid Oxide Compound)

[0150] Four samples of grade 952 silica support were impregnated withabout two times their weight of an aqueous solution containing varyingquantities of ammonium fluoroborate (NH₄BF₄) to produce fluorided,boron-containing solid oxide compounds. The exact quantities are listedin Table 2. Each sample was then dried under vacuum at 120° C.overnight. Each of these fluorided, boron-containing solid oxidecompound samples was divided into smaller samples, each of which wascalcined in dry air for three hours at various temperatures to producetreated solid oxide compounds. These treated solid oxide compoundsamples were then tested for polymerization activity with an organometalcompound and 1 millimole of TEA. Nearly all produced polymer. Table 2lists the various activities observed.

[0151] Inventive Example 10 (Treated Solid Oxide Compound)

[0152] Grade 952 silica obtained from W. R. Grace was calcined in dryair at 600° C. for three hours to produce a calcined silica. Then, 7.2grams of the calcined silica were slurried with an ethyl ether solutioncontaining 7.2 millimoles of anhydrous fluoroboric acid (HBF4) toproduce a treated solid oxide compound. The ether was removed by blowingdry nitrogen over the slurry, and finally, the treated solid oxidecompound was warmed under flowing nitrogen to about 60° C. A 0.3283 gramsample of the treated solid oxide compound was charged to the reactorwith TEA and an organometal compound. After about 66.4 minutes, thetreated solid oxide compound produced 54 grams of polymer, giving anactivity of 150 grams of polymer per gram of treated solid oxidecompound per hour (g/g/h).

[0153] The remainder of the treated solid oxide compound was thencharged to the quartz tube for calcining and warmed under dry nitrogento 250° C. where it was held for 3 hours. A 0.0291 gram sample wascharged to the reactor with TEA and an organometal compound. After about69.0 minutes, it produced 37 grams of polymer, giving an activity of 350grams of polymer per gram of treated solid oxide compound per hour.TABLE 1 Calcining Test Test Temp. Compound Polymer Run Time ActivityExample Compound* (° C.) (grams) (grams) (minutes) *(g/g/h)  1 ControlNone 0.0000 0 61.1 0  2 Control Silica 600 0.5686 0.65 63.0 1  3 ControlFluorided Silica 450 0.4350 0 24.5 0  4 Control Silica-Bona 400 0.52364.7 45 12  5 Inventive Treated solid 300 0.0552 22 48.2 496 oxidecompound  6 Inventive Treated solid 400 0.1642 44 52.7 305 oxidecompound  7 Inventive Treated solide 500 0.1027 12 43.6 161 oxidecompound  8 inventive Treated solid 250 0.4207 247 64.8 544 oxidecompound 10 inventive Treated solid 600 0.3283 54 66.4 150 oxidecompound

[0154] TABLE 2 (Example 9) Amount of Calcining NH₄BF₄ Temp. SilicaPolymer Run Time Activity* (mmol/g*) (° C.) (grams) (grams) (minutes)(g/g/h) 0.3 400 0.1088 5.2 30.0 96 0.3 550 0.1133 40.0 30.0 706 0.3 7000.1272 1.2 30.0 19 0.5 200 0.0850 31.0 30.0 729 0.5 300 0.1100 37.0 30.0673 0.5 400 0.1071 50.0 30.0 934 0.5 500 0.1196 82.0 36.0 1143 0.5 6000.1039 12.1 30.0 233 0.5 700 0.1220 2.3 30.0 38 1.0 550 0.1667 126.061.9 733 1.0 450 0.0803 60.0 61.8 725 1.0 300 0.1230 39.0 18.0 1057 3.0280 0.0753 44.0 61.8 567 3.0 350 0.0523 14.0 58.5 275 3.0 450 0.062314.0 71.9 188 3.0 550 0.0542 0.0 28.0 0

[0155] While this invention has been described in detail for the purposeof illustration, it is not intended to be limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof

That which is claimed is:
 1. A process to produce a catalystcomposition, said process comprising contacting an organometal compound,an organoaluminum compound, and a treated solid oxide compound toproduce said catalyst composition, wherein said organometal compound hasthe following general formula: (X¹)(X²)(X³)(X⁴)M¹ wherein M¹ is selectedfrom the group consisting of titanium, zirconium, and hafnium; wherein(X¹) is independently selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls; wherein substituentson said substituted cyclopentadienyls, substituted indenyls, andsubstituted fluorenyls of (X¹) are selected from the group consisting ofaliphatic groups, cyclic groups, combinations of aliphatic and cyclicgroups, silyl groups, alkyl halide groups, halides, organometallicgroups, phosphorus groups, nitrogen groups, silicon, phosphorus, boron,germanium, and hydrogen; wherein at least one substituent on (X¹) can bea bridging group which connects (X¹) and (X²); wherein (X³) and (X⁴) areindependently selected from the group consisting of halides, aliphaticgroups, substituted aliphatic groups, cyclic groups, substituted cyclicgroups, combinations of aliphatic groups and cyclic groups, combinationsof substituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic groups and substituted cyclic groups, amidogroups, substituted amido groups, phosphido groups, substitutedphosphido groups, alkyloxide groups, substituted alkyloxide groups,aryloxide groups, substituted aryloxide groups, organometallic groups,and substituted organometallic groups; wherein (X²) is selected from thegroup consisting of cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, substituted fluorenyls,halides, aliphatic groups, substituted aliphatic groups, cyclic groups,substituted cyclic groups, combinations of aliphatic groups and cyclicgroups, combinations of substituted aliphatic groups and cyclic groups,combinations of aliphatic groups and substituted cyclic groups,combinations of substituted aliphatic groups and substituted cyclicgroups, amido groups, substituted amido groups, phosphido groups,substituted phosphido groups, alkyloxide groups, substituted alkyloxidegroups, aryloxide groups, substituted aryloxide groups, organometallicgroups, and substituted organometallic groups; wherein substituents on(X²) are selected from the group consisting of aliphatic groups, cyclicgroups, combinations of aliphatic groups and cyclic groups, silylgroups, alkyl halide groups, halides, organometallic groups, phosphorusgroups, nitrogen groups, silicon, phosphorus, boron, germanium, andhydrogen; wherein at least one substituent on (X²) can be a bridginggroup which connects (X¹) and (X²); wherein said organoaluminum compoundhas the following general formula: Al(X⁵)_(n)(X⁶)_(3−n) wherein (X⁵) isa hydrocarbyl having from 1 to about 20 carbon atoms; wherein (X⁶) is ahalide, hydride, or alkoxide; and wherein “n” is a number from 1 to 3inclusive; wherein said treated solid oxide compound comprises fluorine,boron, and a solid oxide compound; wherein said solid oxide compoundcomprises silica, and there is a substantial absence of titanium andzirconium.
 2. A process to produce a catalyst composition comprising: 1)contacting silica with an aqueous solution containing ammoniumfluoroborate or fluoroboric acid to produce a fluorided,boron-containing solid oxide compound having from 1 to 3 millimoles ofboron per gram of fluorided, boron-containing solid oxide compoundbefore calcining and having from 4 to 25% by weight fluorine based onthe weight of said fluorided, boron-containing solid oxide compoundbefore calcining; 2) calcining said fluorided, boron-containing solidoxide compound at a temperature within a range of 250 to 500° C. for 3to 20 hours to produce a calcined composition; 3) combining saidcalcined composition and bis(n-butylcyclopentadienyl) zirconiumdichloride at a temperature within a range of 15° C. to 50° C. for 1minute to 1 hour to produce a mixture; and 4) combining said mixture andtriethylaluminum to produce said catalyst composition.
 3. A processaccording to claim 2 wherein said process consists essentially of steps(1), (2), (3), and (4).
 4. A catalyst composition produced by saidprocess of claim
 1. 5. A catalyst composition according to claim 4wherein said catalyst composition has an activity greater than 500 gramsof polymer per gram of treated solid oxide compound per hour underslurry polymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and a pressure of 550 psig.
 6. Aprocess according to claim 5 wherein said catalyst composition has anactivity greater than 1000 grams of polymer per gram of treated solidoxide compound per hour under slurry polymerization conditions, usingisobutane as a diluent, with a polymerization temperature of 90° C., anda pressure of 550 psig.
 7. A catalyst composition according to claim 5wherein a weight ratio of said organoaluminum compound to said treatedsolid oxide compound in said catalyst composition ranges from about 3:1to about 1:100.
 8. A catalyst composition according to claim 7 whereinsaid weight ratio of said organoaluminum compound to said treated solidoxide compound in said catalyst composition ranges from 1:1 to 1:50. 9.A catalyst composition according to claim 5 wherein a weight ratio ofsaid treated solid oxide compound to said organometal compound in saidcatalyst composition ranges from about 1000:1 to about 10:1.
 10. Acatalyst composition according to claim 9 wherein said weight ratio ofsaid treated solid oxide compound to said organometal compound in saidcatalyst composition ranges from 250:1 to 20:1.
 11. A catalystcomposition according to claim 10 wherein said treated solid oxidecompound comprises silica, 1 to 3 millimoles of boron per gram oftreated solid oxide compound before calcining, from 4 to 25% by weightfluoride based on the weight of said treated solid oxide compound beforecalcining, and is calcined for 3 to 20 hours at a temperature from 250to 500° C.
 12. A catalyst composition comprising a post-contactedorganometal compound, a post-contacted organoaluminum compound, and apost-contacted treated solid oxide compound comprising boron, fluorine,and a solid oxide compound.
 13. A polymerization process comprisingcontacting at least one monomer and said catalyst composition of claim 4under polymerization conditions to produce a polymer.
 14. A processaccording to claim 13 wherein said polymerization conditions compriseslurry polymerization conditions.
 15. A process according to claim 14wherein said contacting is conducted in a loop reaction zone.
 16. Aprocess according to claim 15 wherein said contacting is conducted inthe presence of a diluent that comprises, in major part, isobutane. 17.A process according to claim 13 wherein at least one monomer isethylene.
 18. A process according to claim 13 wherein at least onemonomer comprises ethylene and an aliphatic 1-olefin having 3 to 20carbon atoms per molecule.
 19. An article that comprises said polymerproduced according to claim 13.